Tar-bonded refractories containing pine tar



3,340,075 Patented Sept. 5, 1967 3,340,075 TAR-BONDED REFRACTORIES CONTAINING PINE T AR Stuart V. Stoddard, Needham, and John F. Hardy and be ground to particulate form and handled as a powder and which do not substantially soften at temperatures below those at which the green composition will be produced, i.e. do not soften at temperatures from below about Porter F. Gridley, Andover, Mass., assignors to Cabot 5 room temperature about p uPoll Corporation, Boston, Mass., a corporation of Delaware Poo g or blending temperatures 1n a g ease; can be No Drawing. Filed Dec. 16, 1964, Ser. No. 418,865 utilized in combrnatlon with other particulate solids. The

Claims. (Cl. 106-56) average particle size of the solid utilized is not critical, sizes between about 44 microns and about in. being This invention r la s t novel oarhoh-oontahltrlg 10 normally entirely satisfactory. In addition as is well Positions and more sPeeifieeny to hovel tar-bonded known, the solids utilized should be substantially free of fractories comprising a particulate solid and a binder. moisture Compositions Comprising a Particulate refractory Solid Any hydrocarbonaceous material which is liquid and and a binder are well known and useful articles Of COlIlhas a viscosity at room temperature of at least about merce- Thus, compositions comprising dolomite ss 8,000 cps. and preferably above about 10,000 cps., or gates, Perielase fines and an organic binder are often hydrocarbonaceous materials which are solid at room temo ke in the Substantial ahserlee of oxygen to Produce perature but which are liquid or semi-liquid at comtar-bonded refractory materials as disclosed for example, pounding 0 blending temperatures, i.e. at temperatures in III finished materials of this yp green up to about 400 F., and which materials can be coked at strength and density are extremely important fac o s- It elevated temperatures, i.e. at temperatures above about has been found, for p that g green Strength 600 F. and normally above about 1000 F., to yield at uits in a minimum of damage to molded arti s d to least about 20%, and preferably at least about 50% by handling, transportation and the like Whereas density is Weight thereof of carbon are normally suitable as a bindrelated to servieeahihty, he the higher the y, the er component for the purposes of the present invention. longer the service life. Typical hydrocarbonaceous materials suitable for the pur- IH-aeoordahee with the Present invention, there are P poses of the present invention include coal tar pitch, Vided improved Compositions Which have improved green petroleum pitch, low molecular weight polyethylenes and strengths and higher densities. other polyolefins, asphaltenes, heavy fuel oils, for exam- A g y, it is a principal object f the present ple, Bunker c, molasses, and many other materials and Vehtiorl to Provide improved compositions Comprising a mixtures thereof which are obvious to one skilled in the particulate solid and a binder. art. Needless to say, hydrocarbonaceous materials which It is another object of the present invention to provide upon being coked yield undesirable or deleterious resioorrllrositiohS comprising a Particulate refractory Solid and dues such as sulfur should be avoided. In particular, howan organic hi d r hi h mp i i n have g green ever, hydrocarbonaceous materials such as coal tar pitch, strengths and high d nsiti s petroleum pitch, and asphaltenes are greatly preferred.

It is amother object of the Present invention to Provide Pine tar is a complex mixture of twenty or more comimprov tar-bonded refractory oompositiorlspounds and is derived from the destructive distillation of Other Objec Of h pres invention l in P he pine tree stumps and/ or pine tree heart Wood. Recent obvious and will in part appear hereinafter. work in fractionating pine tar indicates that about 25% In accordance With the Present invention it s by weight of the pine tar consists of resin acids such as covered that When in produ ing rd refractory abietic, dehydroabietic, di-pimaric and iso-7-d-pimaric compositions comprising a particulate refractory solid and id d b t 25% t 35% b i h consists f a hinder, the binder Comprises y Weight between about 5 identified phenolics and polymeric phenolics. The remainand about 60%, n Preferably between about 10 and ing portion of the pine tar, about 40%, consists of neutral pine tar and between about 40 and and prefcompounds (ketones, alcohols, hydrocarbons, etc.), none erably between about 50 and 90% Of a heavy hydrocarof which alone are present in very large amounts, bonaceous material, the resulting compositions possess un- Broadly speaking, the present invention contemplates expectedly high green strengths and densities both before the term pine tar to mean the liquid product obtained and after coking. 50 from the destructive distillation of pine tree stumps Particulate refractory solids suitable for the purposes and/or pine tree heart wood. However, in commercial of the present invention are generally well known to the practice the crude pine tar recovered after destructive art and in any case are not critical. Typical solids that distillation is often subjected to a refining operation and can be utilized are dolomite (CaO.MgO), lime (CaO), those fractions which have boiling points between about magnesia, chrome ore, silica and mixtures thereof. In 55 C. and 355 C. or somewhat higher normally repreaddition, high melting point pitches and tars which can sent present commercial pine tars. The viscosity of the TABLE I Pine Tar Oil Light Pine Medium Pine Heavy Pine (PT-101) Tar (PT-400) Tar (PT-600) Tar (PT-s00) s Gr. at 15 C 1.030-1.140 1. nee-1.070 1.005-1. 075 1. 075-1. 080 Flash Point (open cup),

F 136 181 257 265 Acidity (as acetic acid) percent max 0.15 0. 15 0.1 0.1 Viscosity (Brookfield at 30 0.), cps 98-141 500-900 1,7002,650 asso-7,400 Acid No 40-45 50-60 55-60 55-65 Color 1 Spindle No. 1. 2 Spindle No. 4.

8 Golden brown;

3 particular fraction will determine its designation as a light, medium or heavy pine tar. The dehydrated material which is removed at temperatures below about 120 C. is generally referred to as the light ends and is essenabout 6% of a coal tar pitch having a softening point of about 250 F. Two 75 gram samples of the resulting composition are pressed into brick form as in Example 1 and the resulting bricks are treated and tested as in tially terpenoid in nature. The present invention con- Example 1. The results are reported in Table H below. templates the use of crude pine tar and/or the ab-ove- Exam le 4 mentioned refined fractions. The above table illustrates p the properties of various commercially available pine tars A composition is prepared which is a duplicate of the produced by Cabot Corporation. composition of Example 3 except that in place of .said It is to be understood that resinous products of pine 10 6% of coal tar pitch there is utilized in this example tree stumps and heart wood having properties somewhat about 5.4% of said pitch having a softening point of similar to those enumerated above but obtained by way about 250 F. and 0.6% of PT101 pine tar. Two 75 of solvent extraction processes or otherwise can oftengram samples of the resulting composition are pressed times be used in the practice of our invention. Accordinto brick form as in Example 1 and the resulting bricks ingly, it is intended that such products be included within are treated and tested as in Example 1. The results are the scope of the term pine tar. reported in Table II below.

TABLE II Sample From Percent Percent Percent Compressive Example Total Coal Tar Pine Treatment Strength Density Binder Pitch Tar (p.s.i.)

6 6.0 0 Green 6 6.0 0 Coked 6 5.4 0.6 Greern. 6 5.4 0.6 Coked 6 6.0 0 Green 6 6.0 0 Coked. 6 5.4 0.6 Green 6 5.4 0.6 Coked The-total quantity of binder, i.e., comprising both the hydrocarbonaceous material and pine tar utilized in producing the improved tar-bonded refractories of the present invention is not critical bearing in mind of course that the green composition must have a consistency that renders itmoldable to produce acceptable shaped articles. Normally, however, total binder concentrations between about 3% and and preferably between about 5% and 15 by weight of the total green composition have been found to be suitable.

There follow a number of non-limiting illustrative ex amples:

Example 1 A composition comprising by weight about 24% +5 mesh dolomite, 24% 5+20 mesh dolomite, 9.8% -20 mesh dolomite, 37% periclase fines and 6% of a liquid coal tar pitch having a softening point of about 158 F. was produced by'heating each of the ingredients to about 350 F. and then blending them together. Two 75 gram samples of the resulting composition were then pressed to brick form under 10,000 lbs. pressure in a conventional 2" x 4" x 12" steel mold. One brick was not treated further but after 24 hours, was tested for compressive strength and the density thereof was measured. The other brick was coked in a graphite bed wherein the temperature was raised at the rate of 140 F./-hr. until the temperature reached about 1800 F. at which temperature the bed was maintained for about 2.5 hours. The coked sample was then cooled and the density thereof was measured. The data obtained appears in Table I below.

Example 2 tested as in Example 1.,The results are reported in Table II below.

Example 3 A composition is prepared which is a duplicate of the composition of Example 1 except that in place of said 6% of coal tar pitch, there is utilized in this example It will be noted by reference to Table II that equivalent compositions comprising an equivalent quantity of total binder but wherein the binder comprises pine tar possesses both higher compressive strengthsrand higher densities.

Obviously, many changes can be made in the above examples without departing from the scope of the present invention. For example, while for convenience-only two difierent refractory solids were utilized in all of the above examples, any of the other solids mentioned heretofore would normally be entirely suitable for the purposes of the present invention.

Also, the refractory compositions of the present invention can contain any of the materials such as carbon black, for example, as disclosed is copending U.S. application Ser. No. 405,271, filed Oct. 20, 1964 by John F. Hardy et aL, which can normally be added to tar-bonded refractory compositions. Thus, for example, therefra-ctory compositions of the present invention can comprise furnace blacks, channel blacks, acetylene blacks and/or lamp blacks.

Accordingly, it is intended and it should be understood that the above disclosure is illustrative in nature and is not to be construed as limiting the scope ofthe present invention.

What we claim is:

1. A novel composition which consists essentially of 85 to 95% of a particulate refractory solid selected from the group consisting of dolomite, lime, magnesia, chrome ore, silica and mixtures thereof and 5 to 15% of a binder which is by weightrbetween about 5 and about 60% pine tar and between about 40 and about of a hydrocarbonaceous material selected from the group consisting of coal tar pitch, petroleum pitch, asphaltenes, solids convertible to a liquid state at temperatures below about 400 F., heavy oils of at least 8,000

cps. viscosity, and mixtures thereof.

2. The composition of claim 1 wherein said binder upon coking in the substantial absence of oxygen yields at least about 50% by weight thereof of carbon.

3. The. composition of claim 1 wherein said binder comprises between about 10% and about 50% pine tar.

4. The composition of claim 1 wherein the pine tar utilized is produced by destructive disttllation.

5. The composition of claim 1 wherein said hydrocarbonaceous material is chosen from the group consisting of coal tar pitch, petroleum pitch and asphaltenes.

6. The composition of claim 1 wherein said hydrocarbonaceous material is coal tar pitch.

7. A process for producing an improved refractory material which comprises molding a composition consisting essentially of 85% to 95 of a particulate refractory solid selected from the group consisting of dolomite, lime, magnesia, chrome ore, silica and mixtures thereof and 5 to 15% of a binder which is by weight between about 5 and about 60% pine tar and between about 40 and about 95% of a hydrocarbonaceous material selected from the group consisting of coal tar, pitch, petroleum pitch, asphaltenes, solids convertible to a liquid state at temperatures below about 400 F., heavy oils of at least 8,000 cps. viscosity, and mixtures thereof, and heating the molded article to temperatures above about 1000 F. in the substantial absence of oxygen.

8. The process of claim 7 wherein said binder upon coking yields at least about 50% by weight thereof of carbon.

References Cited UNITED STATES PATENTS 3/1879 Thomas 106-58 3/1964 Spetzler et a1. 106-58 TOBIAS E. LEVOW, Primary Examiner.

I. E. POER, Assistant Examiner. 

1. A NOVEL COMPOSITION WHICH CONSISTS ESSENTIALLY OF 85 TO 95% OF A PARTICULATE REFRACTORY SOLID SELECTED FROM THE GROUP CONSISTING OF DOLOMITE, LIME, MAGNESIA, CHROME ORE, SILICA AND MIXTURES THEREOF AND 5 TO 15% OF A BINDER WHICH IS BY WEIGHT BETWEEN ABOUT 5 AND ABOUT 60% PINE TAR AND BETWEEN ABOUT 40 AND ABOUT 95% OF A HYDROCARBONACEOUS MATERIAL SELECTED FROM THE GROUP CONSISTING OF COAL TAR PITCH, PETROLEUM PITCH, ASPHALTENES, SOLIDS CONVERTIBLE TO A LIQUID STATE AT TEMPERATURES BELOW ABOUT 400*F., HEAVY OILS OF AT LEAST 8,000 CPS. VISCOSITY, AND MIXTURES THEREOF. 